Coating composition



Patented Jan. 16, 1945' con'rnve 'ooMPosrrroN Rector, Fort Worth, and Charles LI Laurence L Cron, Houston, Tex. I

No Drawing. Application July 24, .1941,

- Serial No. 493,868 1 5Claims. (01.106-171).

This invention relates to new and useful improvementsin coating compositions.

This application is ajcontinuation-in-part of our co-pending application, Serial No. 296,446, filed September 25, 1939.

In the production and refining of petroleum thereare many instances where it is necessary to store the petroleum or its fractions. This storage is usually in metallic tanks and a serious corrosion problem is thereby encountered. Nearly all crude oil contains dilute acids, salt water, and other materials which corrode iron and steel rapidly. Even wood is not entirely immune to the attack of these corrosive substances. There are also many other instances in this and various other industries where it is desirable to protect tanks and pipe lines against corrosion;

A roblem that occurs in almost as many instances as corrosion, is the deposition of parafiin from petroleum onto the walls of tubing and tanks. Tanks mustbe i'requently cleaned out to remove the parafiin from the walls thereof. Simv ilarly, tubing and pipe lines must be scraped or reamed to remove paraifin deposits from the inside tllereof.

.One object of-the invention is to provide coatmg compositions-suitable for coating the ini side of storage tanks, which will efifectively seal the inside of said tanks, and prevent the same from leaking and causing material stored therein to be lost or wasted. a

Another'object of the invention is to provide an improved coating composition which is suitable for coating the inside 'of storage tanks, and I which in its initial state before application possosses suflicient fluidity as to allow its easy application; a

A further object of the invention is to'provide an improved coating composition which, after .application'and upon standing, dries and harding in the operation of'said equipment, and

allowing the-tanks to empty clean.

A further object of the invention is toprovide an improved coating composition which will protect the insideof' water tanks against corrosion, an d may 'be used in a variety of other instances to protect tanks and pipes against corrosion. I

Another object of .the invention is to provide a composition of the character described, which includes a base solution consisting of a-cellulose derivative dissolved in a group of liquid solvents, such as esters and ketones, the solvents having a given range, whereby when evaporation occurs, the rate of evaporation is uniform and gradual, with the result that the composition changes from its original free flowing consistency to a plastic mass which will not flow of its own accord or under considerable pressure, and the of evaporation, as would be the case if only one solvent of a low boiling point was employed.

A still further object of the invention is to provide an'improved coating composition wherein the base solution has a softener or plasticizer admixed therewith in excessive amounts; that is, the amount of plasticizer exceeds the retentivity point of the final state of the composition, whereby upon standing oraging, the excess plasticizer' will slowly exude from the composition to. provide a protective fllm of lubricant on the surface of said composition, said film of lubricant being desirable to maintainv the plasticity of the composition.

In producing the improvedcomposition,'.any v derivative of cellulose, such as a salt (cellulose nitrate). an'organic ester (cellulose acetatel or cult to a pliable, elastic mass, whereby it never reaches a hard brittle state but retains suificlent plasticity as to allow it to expand and contract with the tank, thereby eliminating cracking and pping of said composition.

An important object of the invention is to provide an improved coating composition which is waterproof and is also unaffected by petroleum, or any of its fractions, and which will protect the inside of tanks, tubing and pipelines against the corrosive action of salt water, dillltQ'MidS,

and other corrosives occurring in crude oil.

' Another important object of the invention is p to provide j an improved coating composition .which when placed on a surface will prevent the deposition of paraflln from petroleum upon said surface, whereby storage ma-sucker rods, and similar. equipment may be coated byv said composition" and .kept clean, 3 from all deposits, thereby materially aid,-

tanks, piP lines, well an ether (ethyl'cellulose or benzyl cellulose) is employed. Forthe purpose of this description, cellulose nitrate, .which is also known as" nitrocellulose, will be used, but it is'to be understood that any derivative ofcellulose may be substituted therefor.

-The cellulose nitrate is dissolved in a liquid solvent or group of solvents. the dissolution being affected during thorough agitation or mixing. 'The liquid solvents may be esters and ketonc which vary in boiling points over -a relatively .wide range, as for exam le, [from degrees F.

to 300 degrees F. As explained, the cellulose nitrate is dissolved in'this group of solvents to form a base solution, and the proportion of the cellulose derivative to the solventsis suchthat capable of flowing. It has been found that ,a base solution containing aboutytwelve per cent of: the cellulose derivative has -asuitableconsistency; but the inventionlishotto belimitcd boiling points which vary from low to high over 'solution will not become dry or brittle because said solution has body but is quite mobile, being lulose nitrate and, therefore,

to this figure, as theproportions may vary without defeating the purpose of the invention.

The base solution so formed is made up of a cellulose derivative in solution in a series of solvents. This'series of solvents ranges in boiling points from a fairly low temperature, 50 to 100 degrees F.', to a fairly high temperature, 200 to 400 degrees F. These temperature ranges are stated merely to give an idea of the range andv having the lower boiling points, will evaporate:-

while'the heavier, or higher boiling point, solvents will, not-evaporate even under considerable heat, and they maintain the composition in an elastic condition. It will be seen that the final or terminal consistency of the composition may be determined beforehand by varying the proportions of the lighter and theheavier solvents. Also, it is obvious that the composition will not .become caked or brittle but will be held in an elastic condition indefinitely by the action of the high boiling solvents. The elasticity of the compound is not sufiicient as to allow it to fiow of its own accord or under pressure, but it is sufficient as to prevent the compound from caking or chipping under conditions of vibration. The higher boiling solvents used are essentially nonsoluble in etroleum or its fractions, whereby the compound may not be dissolved or disintegrated by said petroleum, and is ideal for use in tanks .to be used for the storage of petroleum and It is pointed out that the comits fractions. pound and its ingredients are also insoluble in water, whereby the composition may be" used to protect water lines and tanks, and steam lines.

Resin is then added to the base solution to add body and adhesiveness to the composition. The resin added is preferably one which is insoluble in petroleum; shellac, for example, could be used. The addition of the resin has very little effect on the viscosity of the composition and serves to add-,film-forming material to the composition, whereby the tank or pipe line coated with the composition is more completely protected. Resin may be added in quantities equal in weight up to 10o per cent of the weight of the cellulose.

The base solutimi, consisting of the cellulose with stirring. It is pointed out that the invention is not to be limited to blown castor oil, and that any polymerized or oxidized oil may be used, provided it is insoluble in petroleum and its fractions. Any softener or plasticizer having characteristics similar to those of blown cas tor oil may 'be employed. Whatever plasticizer is used, is always added in such amounts as to exceed the retentivity oint of the particular cellulose derivative for that softener.

The oil or softener is added to the base solution preferably in an amount equal in weight to three to five times the weight of the cellulose derivitive, although these proportions may vary. While the exact amount of softener or plasticizer which is added to the base solution is subject to variation, it is desirable that sufficient softener or plasticizer be added so as to exceed the point of retentivity of the cellulose nitrate. Thus, when the mixture is allowed to stand, the softener or plasticizer slowly exudes from the mixture. Thisexudin'g plasticizer, which is the blown vegetable oil,- forms a thin protective film on the outer surface of the compound, as will be more fully explained. The excess plasticizer is carried in the composition in minute particles "much as the oil is carried in a stable oil-water emulsion. This suspension is very stable and the plasticizer does not commence to exude or "sweat out of the composition until the composition has lost a part of its solvents by evaporation and has hardened to its final state. The additionof the blown vegetable oil functions in the compound to prevent-drying beyond a given or predetermined point and adds body to the composition.

After the base solution and softener or plastioirer (castor oil) are admixed, a suitable bulk-,

. ing agent, such as a mineral filler, is added. The

filler is inert, insoluble in water, petroleum, salt water, and dilute acids. The filler is preferably added in amounts suflicient to give the composition in its final or hardened state the desired consistency. It has been found that such con-,-. sistency is obtained by adding the filler in amounts equal to from fifteen to twenty-five per cent of the total weight of the liquid, depending upon the density of the filler used. Although any M a suitable mineralfiller may be employed, a filler or pigment such as asbestine," clay, graphite,

nitrate and the group of solvents plus the resin, Y

is next admixed with a plasticizer or softener, the latter being preferably added to the solution while stirring. The plasticizer or softener is one I of very low solubility in petroleum hydrocarbons,

desirable that the castor oil be to'avoid this it ii,'

added'slow yand u talc, or the like, may be employed, and it is preferable that the filler be finely ground so as to give the mixture a smooth texture. The filler or pigment is added to the composition for the of making saidcomposition opaque.

This is necessary because the person applyingthe coating must be-able to ascertain which portions of the surface have' been cooled and which have not. If the composition were left in a clear conditiomthis would be impossible. A mineral filler has been found'entirely'satisfactory.

. but other equivalent fillers, capable of the same function in the.compositlon, could 'bei used.

The low-boiling solvents usedin making up I, the base solution are added in sufficient amounts as to carry'the filler and maintain the composition in a fluid state. whereby it may be sprayed. As hereinbefore set forth, the lighter solvents evaporate from the composition as it hardns.

Therefore-any desired amount of light solvents may be used without departing from the, principle taught by the invention.

In order to prevent the mineral from settling' in the liquid during storage, a suitable suspending agent, such as aluminum stearate. magnesium linolenate, or the like, may be added'although this is not essential. 1 J

"In use, the composition is applied to the inside surface of '-a tank,- tubing, or anyother surface which it is desiredto protect. Although this application maybe by means of "a spray gun or by a brush, it has been 'found'that the spray gun method is the most satisfactory. The composition is sufiiciently fluid to allow this applicationfand 'may be made even more fluid by the addition of more light solvent or thinner. As the composition sets, the lighter solvents evaporate therefrom, thus allowing the composition to attain a soft pliable consistency, which is 'not mobile, and will not allow the composition to flow of its own accord or under considerable pressure. The presence of the plasticizer or softener and the high boiling solvents in the composition prevents the composition from drying or As has been previously pointed out, the softener or plasticizer (blown castor oil) is admixed.

steam lines.

' Parts Cellulose nitrate 40 Blown castor oil o 200 Pigment and possibly a trace of amyl acetate.

The composition has been found particularly adaptable for use in the petroleum industry, as it is substantially unaffected by dilute acids, gas, gasoline, or other petroleum hydrocarbons; it is also waterproof-and is capable ofwithstanding high pressure, as well as high temperatures. Although it has been used satisfactorily in the petroleum industry for protecting metal tanks and othersurfaces that come in contact with crude oil and its fractions, it may be used elsewhere. The constituents in the composition'are insoluble in water, as well as insoluble in petroleum, as above explained, and thereby form an effective coating composition for water tanks and Another very important function of the coating composition 'is its prevention of paraflin 'formation.- Tanks, tubing, pipelines, sucker rods, and similar equipment may be coated with this composition, whereby the formation of paraflin deposits thereon will be substantially elimwith the base solution in an amount which is in excess of. the retentivity point of. the cellulose nitrate. When the composition is applied to the surface and allowed to stand, the excess of the plasticizer slowly exudes from the compound, and

such exudation forms-a thin film of said plasticizer, in this instance, blown castor oil, on the surface of the composition. This film or coating of blown castor oil serves to give additional protection to the tankand maintains the plasticity of the composition after it has set.

A specific example of the portions of the in-' 40 gradients used in the composition is given as follows:

Parts Cellulose nitrate 40 Acetone 132 Ethyl acetate 441 "Benzol 7 144.8 Glycerol triacetate 5 Blown castor oil 200 Pigment 25 which example after setting would have ap proximately the following composition:;

. Parts Cellulose nitrate 40 Blown castor oil 200 Pigment 25 Another example-of the proportions of the ingredie'nts ,used in the compositionis given as .This example after hardening or settin would have approximately the following compopzition: I v

inated. Thus, the composition carries out two very important functions. It protects asurface against corrosion and prevents the deposition of paraflin thereon.

In conjunction with coating by this composition, it has been found thatthe coating tends to present a smooth surface to the. interior of the tubing'or pipe coated, and thereby reduces friction losses in said pipe when liquid is being pumped therethrough.

'lution comprising a cellulose derivative selected from the group consisting of cellulose nitrate, cellulose acetate, ethyl cellulose and benzyl cellulose dissolved in a series of liquid solvents, a

portion of'which solvents will evaporate as the composition sets, blown castor oil admixed with the base solution in such high proportions as to exceed the retentivity of the setcomposition,

whereby as the composition hardens after application the excessblown'castor oil will exude from the composition and said composition will remain in a moist plastic state, the blown castor oil being compatible with the base solution in all proportions and compatible in limited proportions only 1 with the cellulose derivative. i

cellulose nitrate, cellulose acetate, ethyl cellulose and benzol cellulose in the. amount of 3-5%,

13% to 15% acetone, 40% to 50% ethyl acetate, 10% to 20% benzol, at least 25% glycerol triaoetataand 15% to 25%. blown castor oil.

" 5. A coating composition including, a baseso lutlon comprising acellulose derivative selected from the group consisting of cellulose nitrafte, cellulose acetate, ethyl cellulose and benzyl cellulose dissolved in a series of liquid solvents, a

portion of which solvents will evaporate as the composition sets, blown non-drying vegetable oil admixed with the base solution in such high proportions as to exceed the retentivity of the set composition, whereby as the composition hardens I after application the excess blown non-drying LAURENCE L. RECTOR. CHARLES L. CRON, 

